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JPH04101305A - Resin compound for electric insulation and insulated electric wire - Google Patents

Resin compound for electric insulation and insulated electric wire

Info

Publication number
JPH04101305A
JPH04101305A JP2218518A JP21851890A JPH04101305A JP H04101305 A JPH04101305 A JP H04101305A JP 2218518 A JP2218518 A JP 2218518A JP 21851890 A JP21851890 A JP 21851890A JP H04101305 A JPH04101305 A JP H04101305A
Authority
JP
Japan
Prior art keywords
series resin
resin composition
alcohol component
parts
polyester series
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2218518A
Other languages
Japanese (ja)
Inventor
Akira Uchiyama
明 内山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Corp
Original Assignee
Hitachi Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Priority to JP2218518A priority Critical patent/JPH04101305A/en
Publication of JPH04101305A publication Critical patent/JPH04101305A/en
Pending legal-status Critical Current

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  • Polyurethanes Or Polyureas (AREA)
  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)

Abstract

PURPOSE:To provide an insulated electric wire having a heat resistance over Class B, which assures good soldering performance and is equipped with excellent anti-softening property, by allowing the material to contain stabilized isocyanate compound and polyester series resin obtained through reaction of specific alcoholic components with multi-basic acids. CONSTITUTION:The material concerned shall contain 100-1000 parts by wt. stabilized isocyanate compound and 100 parts by wt. polyester series resin obtained through reaction of multi-basic acids with alcoholic components, wherein 50-90 equivalent % of all alcoholic components consists in tris (2-hydroxy ethyl) isocyanurate. The polyester series resin is obtained through reaction of alcoholic components with multi-basic acids, wherein the former shall be excessive in the equivalent relative to the latter, and hydroxyl radicals shall preferably remain in the polyester series resin. This provides an insulated electric wire having excellent anti-softening property, soldering performance, and a heat resistance over Class B.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は電気絶縁用樹脂組成物、さら−に詳しくは耐熱
性に優れ、かつはんだ付は性に優れた絶縁電線を得るこ
とができる電気絶縁用樹脂組成物およびこれを用いた絶
縁電線に関する。
[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to an electrically insulating resin composition, and more specifically, to an electrically insulating resin composition that has excellent heat resistance and excellent soldering properties. The present invention relates to an insulating resin composition and an insulated wire using the same.

〔従来の技術〕[Conventional technology]

従来、はんだ付は性を有する絶縁電線として、ポリウレ
タン系の絶縁電線が多く用いられているが、この電線の
耐熱性がA−E種(電気用品取締法による耐熱区分)で
あり、これ以上の耐熱性を必要とする用途には使用でき
ないという欠点があった。
Conventionally, polyurethane-based insulated wires have often been used as insulated wires for soldering, but the heat resistance of these wires is class A-E (heat-resistant classification according to the Electrical Appliance and Materials Control Law), and higher It has the disadvantage that it cannot be used in applications that require heat resistance.

最近、この欠点を改良するため、分子中にイミド結合を
有するポリエステル系樹脂と、トリメチロールプロパン
、グリセリン等のアルコール成分に、トリレンジイソシ
アネートおよびジフェニルメタンジイソシアネートを付
加した後、遊離のイソシアネートをフェノール類でブロ
ックして得られるブロックイソシアネート樹脂とを含む
樹脂組成物を、B種絶縁用の電線に用いることが提案さ
れている。しかしながら、この電線は、従来からB種絶
縁用として汎用されているポリエステル塗料を用いた場
合と比較すると、耐熱軟化性に劣る欠点がある。
Recently, in order to improve this drawback, after adding tolylene diisocyanate and diphenylmethane diisocyanate to a polyester resin having an imide bond in the molecule and an alcohol component such as trimethylolpropane or glycerin, the free isocyanate is removed with phenols. It has been proposed to use a resin composition containing a blocked isocyanate resin obtained by blocking for electric wires for type B insulation. However, this electric wire has a disadvantage in that it has inferior heat softening resistance compared to the case where a polyester paint, which has conventionally been widely used for class B insulation, is used.

近年の市場では、特に耐熱衝撃性、耐軟化性、絶縁破壊
電圧保持率等の耐熱性のより一層の向上が求められてい
る。
In recent years, the market has been demanding further improvements in heat resistance, particularly thermal shock resistance, softening resistance, and dielectric breakdown voltage holding rate.

〔発明が解決しようとする課題〕[Problem to be solved by the invention]

本発明の目的は、前記の従来技術の欠点を解決し、耐熱
軟化性およびはんだ付は性に優れ、かつB種以上の耐熱
性を有する絶縁電線を得ることができる電気絶縁用樹脂
組成物およびこれを用いた絶縁電線を提供することにあ
る。
The object of the present invention is to provide an electrically insulating resin composition capable of solving the drawbacks of the prior art described above, and capable of obtaining an insulated wire having excellent heat softening resistance and soldering properties, and having heat resistance of class B or higher. An object of the present invention is to provide an insulated wire using the same.

〔課題を解決するための手段〕[Means to solve the problem]

本発明は、(A)全アルコール成分の50〜90当量%
がトリス(2−ヒドロキシエチル)イソシアヌレートで
あるアルコール成分と多塩基酸とを反応させて得られる
ポリエステル系樹脂100重量部および(B)安定化イ
ソシアネート化合物100〜1000重量部を含有して
なる電気絶縁用樹脂組成物およびこれを導体上に塗布、
焼付けてなる絶縁電線に関する。
The present invention provides (A) 50 to 90 equivalent% of the total alcohol component.
100 parts by weight of a polyester resin obtained by reacting an alcohol component in which is tris(2-hydroxyethyl) isocyanurate with a polybasic acid, and (B) 100 to 1000 parts by weight of a stabilized isocyanate compound. Insulating resin composition and coating it on the conductor,
Concerning baked insulated wires.

本発明に用いられるポリエステル系樹脂(A)は、アル
コール成分と多塩基酸とを反応して得られる。
The polyester resin (A) used in the present invention is obtained by reacting an alcohol component and a polybasic acid.

アルコール成分は、多塩基酸に対して当量で過剰として
反応させ、ポリエステル系樹脂(A)に水酸基を残存さ
せるのが好ましい。該水酸基は焼付は時に安定化イソシ
アネート化合物(B)と反応してウレタン結合を生成す
る。
It is preferable that the alcohol component is reacted in an equivalent amount in excess with respect to the polybasic acid, so that hydroxyl groups remain in the polyester resin (A). During baking, the hydroxyl group sometimes reacts with the stabilizing isocyanate compound (B) to form a urethane bond.

アルコール成分と多塩基酸の使用割合は、はんだ付は性
および耐熱性の点から、当量比(全アルコール成分/多
塩基酸)で1.6〜2.5の範囲が好ましく、1.6〜
2.0の範囲がより好ましい。
The ratio of alcohol component and polybasic acid used is preferably in the range of 1.6 to 2.5 in equivalent ratio (total alcohol component/polybasic acid) from the viewpoint of soldering properties and heat resistance.
A range of 2.0 is more preferred.

アルコール成分としては、トリス(2−ヒドロキシエチ
ル)イソシアヌレートを全アルコール成分に対して好ま
しくは50〜90当量%、より好ましくは55〜75当
景%とされる。トリス(2−ヒドロキシエチル)イソシ
アヌレートの量が上記範囲外では耐熱性およびはんだ付
性が低下する傾向がある。トリス(2−ヒドロキシエチ
ル)インシアヌレート以外のアルコール成分としては、
例エバエチレングリコール、プロピレングリコール等の
ジオール類、グリセリン、トリメチロールエタン等のト
リオール類などが用いられる。
As the alcohol component, tris(2-hydroxyethyl) isocyanurate is preferably used in an amount of 50 to 90 equivalent %, more preferably 55 to 75 equivalent %, based on the total alcohol component. When the amount of tris(2-hydroxyethyl)isocyanurate is outside the above range, heat resistance and solderability tend to decrease. Alcohol components other than tris(2-hydroxyethyl)in cyanurate include:
Examples include diols such as evaporated ethylene glycol and propylene glycol, and triols such as glycerin and trimethylolethane.

多塩基酸としては、例えばテレフタル酸、テレフタル酸
ジメチル、テレフタル酸モノメチル、テレフタル酸ジエ
チル等のテレフタル酸低級アルキルエステルなどが挙げ
られる。またエナメル線用ポリエステルワニスに常用さ
れる化合物、例えばイソフタル酸、アジピン酸、フタル
酸、セバシン酸等を用いることもでき、さらにイミドジ
カルボン酸を用いることもできる。
Examples of polybasic acids include lower alkyl terephthalic acid esters such as terephthalic acid, dimethyl terephthalate, monomethyl terephthalate, and diethyl terephthalate. Compounds commonly used in polyester varnishes for enameled wires, such as isophthalic acid, adipic acid, phthalic acid, and sebacic acid, can also be used, and imidodicarboxylic acid can also be used.

アルコール成分および多塩基酸はそれぞれ単独でまたは
2種以上組合わせて用いられる。
The alcohol component and the polybasic acid may be used alone or in combination of two or more.

ポリエステル系樹脂(八)の合成は、前記アルコール成
分と多塩基酸を、好ましくは有機溶剤中で、エステル化
触媒の存在下に170〜250℃の温度で加熱反応させ
て行われる。エステル化触媒としては、例えばテトラブ
チルチタネート等のテトラアルキルチタネート、酢酸鉛
、ジブチルスズラウレート、オクテン酸亜鉛、ナフテン
酸亜鉛などが用いられ、また有機溶媒としては、例えば
フェノール、クレゾール、キシレノール等のフェノール
系溶媒が用いられる。
The polyester resin (8) is synthesized by subjecting the alcohol component and polybasic acid to a heating reaction at a temperature of 170 to 250°C, preferably in an organic solvent, in the presence of an esterification catalyst. Examples of esterification catalysts used include tetraalkyl titanates such as tetrabutyl titanate, lead acetate, dibutyltin laurate, zinc octenoate, and zinc naphthenate. Examples of organic solvents include phenols such as phenol, cresol, and xylenol. A system solvent is used.

本発明に用いられる安定化イソシアネート化合物(B)
としては、例えば4.4′−ジフェニルメタンジイソシ
アネートとキシレノールとから得られる化合物(日本ポ
リウレタン工業社製商品名、ミリオネートMS−50)
、4 4 ’−ジフェニルメタンジイソシアネート、脂
肪族ポリオ−・ルおよびフェノール類から得られる化合
物(日本ポリウレタン工業社製商品名、コロネート25
03)、トリレンジイソシアネート、脂肪族ポリオール
およびフェノール類から得られる化合物(バイエル社製
商品名、ディスモジュール APステーブル)等が挙げ
られる。
Stabilized isocyanate compound (B) used in the present invention
For example, a compound obtained from 4,4'-diphenylmethane diisocyanate and xylenol (trade name: Millionate MS-50, manufactured by Nippon Polyurethane Kogyo Co., Ltd.)
, 44'-diphenylmethane diisocyanate, a compound obtained from aliphatic polyol and phenols (trade name, Coronate 25, manufactured by Nippon Polyurethane Industries, Ltd.)
03), a compound obtained from tolylene diisocyanate, an aliphatic polyol, and a phenol (trade name: Dismodur AP Stable, manufactured by Bayer AG).

本発明の電気絶縁用樹脂組成物は、上記したポリエステ
ル系樹脂(A)100重量部および上記した安定化イソ
シアネート化合物(B)100〜1000重量部、好ま
しくは150〜500重量部を含有する。安定化イソシ
アネート化合物(B)の量が100重量部未満でははん
だ付は性が低下し、1000重量部を超えると耐熱性が
低下する。
The electrically insulating resin composition of the present invention contains 100 parts by weight of the above polyester resin (A) and 100 to 1000 parts by weight, preferably 150 to 500 parts by weight of the above stabilized isocyanate compound (B). If the amount of the stabilizing isocyanate compound (B) is less than 100 parts by weight, the soldering properties will decrease, and if it exceeds 1000 parts by weight, the heat resistance will decrease.

本発明の樹脂組成物には、必要に応じて芳香族カルボン
酸または脂肪族カルボン酸の亜鉛、鉛、マンガン等の金
属塩、ジブチルスズジアセテート、ジブチルチンスズジ
ラウレートなどの有機金属化合物を加えることができる
。これらの有機金属化合物は絶縁電線焼付は時の線速を
向上させ、硬化時間の短縮、硬化温度の低下およびはん
だ付は性向上に効果を有する。
Metal salts of aromatic carboxylic acids or aliphatic carboxylic acids such as zinc, lead, and manganese, and organometallic compounds such as dibutyltin diacetate and dibutyltintin dilaurate may be added to the resin composition of the present invention, if necessary. can. These organometallic compounds are effective in improving the wire speed when baking an insulated wire, shortening the curing time, lowering the curing temperature, and improving soldering properties.

本発明の樹脂組成物は、通常、有機溶剤で粘度調製した
後、常法により導体上に直接または他の絶縁皮膜ととも
に塗布し、焼付けして絶縁電線とされる。有機溶剤とし
ては、例えばフェノール、クレゾール、キシレノール、
セロソルブ類、カルピトール類等が用いられる。
The resin composition of the present invention is usually adjusted to have a viscosity with an organic solvent, then applied directly or together with another insulating film onto a conductor by a conventional method, and baked to form an insulated wire. Examples of organic solvents include phenol, cresol, xylenol,
Cellosolves, calpitols, etc. are used.

〔実施例〕〔Example〕

以下、本発明を実施例により詳しく説明する。 Hereinafter, the present invention will be explained in detail with reference to Examples.

なお、例中の%は重量%を意味する。In addition, % in an example means weight %.

実施例1 温度計、撹拌機およびコンデサ付き4つ目フラスコに、
トリス(2−ヒドロキシエチル)イソシアヌレート10
4.4g(1,2当量)、エチレングリコール15.5
g(0,5当量)、テレフタル酸ジメチル97.0g(
1,0当量)、クレゾール54.2gおよびテトラブチ
ルチタネート0.21gを入れ、窒素気流中で200°
Cに昇温しで5時間反応させた。その後、クレゾール1
30.1 gを加え、不揮発分50%のポリエステル系
樹脂溶液Aを得た。
Example 1 In a fourth flask with thermometer, stirrer and condenser,
Tris(2-hydroxyethyl)isocyanurate 10
4.4g (1,2 equivalents), ethylene glycol 15.5
g (0.5 equivalents), dimethyl terephthalate 97.0 g (
1.0 equivalent), 54.2 g of cresol and 0.21 g of tetrabutyl titanate were added, and heated at 200° in a nitrogen stream.
The temperature was raised to C and the reaction was carried out for 5 hours. After that, cresol 1
30.1 g was added to obtain a polyester resin solution A with a nonvolatile content of 50%.

得られたポリエステル系樹脂溶液A100gに、コロネ
ート2503.75g1クレゾール137゜5gおよび
ナフテン酸亜鉛(金属分6%)10.4gを添加し、本
発明の樹脂組成物を得た。
To 100 g of the obtained polyester resin solution A were added 2503.75 g of Coronate, 137.5 g of cresol, and 10.4 g of zinc naphthenate (metal content: 6%) to obtain a resin composition of the present invention.

実施例2 実施例1で得られたポリエステル系樹脂溶液A100g
に、コロネート2503.150 g、クレゾール25
0gおよびナフテン酸亜鉛(金属分6%)16.6gを
添加し、本発明の樹脂組成物を得た。
Example 2 100g of polyester resin solution A obtained in Example 1
, Coronate 2503.150 g, Cresol 25
0 g and 16.6 g of zinc naphthenate (metal content: 6%) were added to obtain a resin composition of the present invention.

実施例3 温度計、撹拌機およびコンデサ付き4つロフラスコに、
トリス(2−ヒドロキシエチル)イソシアヌレート12
1.8g(1,4当量)、エチレングリコール12.4
’g (0,4当量)、テレフタル酸ジメチル97.0
g(1,0当量)、クレゾール57.8gおよびテトラ
ブチルチタネート0.23 gを入れ、窒素気流中で2
00°Cに昇温しで5時間反応させた。その後、クレゾ
ール141.6gを加え、不揮発分50%のポリエステ
ル系樹脂溶液Bを得た。
Example 3 In a four-loaf flask with thermometer, stirrer and condenser,
Tris(2-hydroxyethyl)isocyanurate 12
1.8g (1.4 equivalents), ethylene glycol 12.4
'g (0.4 equivalents), dimethyl terephthalate 97.0
g (1.0 equivalent), 57.8 g of cresol and 0.23 g of tetrabutyl titanate, and 2
The temperature was raised to 00°C and the reaction was carried out for 5 hours. Thereafter, 141.6 g of cresol was added to obtain a polyester resin solution B with a nonvolatile content of 50%.

得られたポリエステル系樹脂B100gに、コロネート
2503.75g、クレゾール137.5gおよびナフ
テン酸亜鉛(金属分6%)10.4gを添加し、本発明
の樹脂組成物を得た。
To 100 g of the obtained polyester resin B, 2503.75 g of Coronate, 137.5 g of Cresol, and 10.4 g of zinc naphthenate (metal content: 6%) were added to obtain a resin composition of the present invention.

比較例1 実施例1で得たポリエステル系樹脂溶液A100gに、
コロネート2503.45g1クレゾール97.5 g
およびナフテン酸亜鉛(金属分6%)7.9gを添加し
て樹脂組成物を得た。
Comparative Example 1 To 100 g of the polyester resin solution A obtained in Example 1,
Coronate 2503.45g 1 Cresol 97.5g
and 7.9 g of zinc naphthenate (metal content: 6%) to obtain a resin composition.

比較例2 市販のポリウレタン電線用ワニス、WD−437(日立
化成工業社製)を比較用として用いた。
Comparative Example 2 A commercially available polyurethane wire varnish, WD-437 (manufactured by Hitachi Chemical Co., Ltd.), was used for comparison.

〈試験例〉 実施例1.2.3および比較例1.2で得られたそれぞ
れの樹脂組成物を用いて下記に示す焼付は条件に従って
直径0.4 mmの銅線に塗布、焼付けを行い、絶縁電
線を作製した。
<Test Example> The resin compositions obtained in Example 1.2.3 and Comparative Example 1.2 were applied and baked on a copper wire with a diameter of 0.4 mm according to the baking conditions shown below. , an insulated wire was produced.

焼付は条件 焼付は炉:横型電熱炉(炉長3m) 炉温  :入口/出口−330°C/380°C線速 
 :25m/分 塗装方法:ダイス7回絞り 得られた絶縁電線の特性をJIS  C3003の5〜
19に従って測定し、結果を第1表に示した。なお、熱
劣化後の絶縁破壊電圧は、JISC3003に準じて作
製した絶縁電線を、200°Cの乾燥器に168時間放
置した後、JIS第1表から、本実施例で得られた組成
物を用いた絶縁電線は、比較例のものに比べ、耐軟化性
および熱劣化後の絶縁破壊電圧の保持率等の耐熱性に優
れるとともに、はんだ付は性にも優れることが示される
Conditions for baking Furnace: Horizontal electric furnace (furnace length 3m) Furnace temperature: Inlet/outlet -330°C/380°C Linear speed
: 25m/min Painting method: The characteristics of the insulated wire obtained by squeezing the die 7 times are JIS C3003 5~
The results are shown in Table 1. In addition, the dielectric breakdown voltage after thermal deterioration was determined by leaving an insulated wire prepared according to JISC3003 in a dryer at 200°C for 168 hours, and then using the composition obtained in this example from JIS Table 1. It is shown that the insulated wire used has excellent heat resistance such as softening resistance and dielectric breakdown voltage retention rate after thermal deterioration, as well as excellent soldering properties, compared to the comparative example.

〔発明の効果〕〔Effect of the invention〕

本発明の電気絶縁用樹脂組成物によれば、はんだ付は性
および耐軟化性に優れた、B種以上の耐熱性を有する絶
縁電線を得ることができる。
According to the electrically insulating resin composition of the present invention, it is possible to obtain an insulated wire that has excellent solderability and softening resistance, and has heat resistance of Class B or higher.

Claims (3)

【特許請求の範囲】[Claims] 1.(A)全アルコール成分の50〜90当量%がトリ
ス(2−ヒドロキシエチル)イソシアヌレートであるア
ルコール成分と多塩基酸とを反応させて得られるポリエ
ステル系樹脂100重量部および (B)安定化イソシアネート化合物100〜1000重
量部を含有してなる電気絶縁用樹脂組成物。
1. (A) 100 parts by weight of a polyester resin obtained by reacting an alcohol component in which 50 to 90 equivalent percent of the total alcohol component is tris(2-hydroxyethyl) isocyanurate with a polybasic acid, and (B) stabilized isocyanate. An electrically insulating resin composition containing 100 to 1000 parts by weight of a compound.
2.全アルコール成分と多塩基酸の使用割合を当量比(
全アルコール成分/多塩基酸)で1.6〜2.5の範囲
とした請求項1記載の電気絶縁用樹脂組成物。
2. The usage ratio of total alcohol component and polybasic acid is equivalent ratio (
2. The electrically insulating resin composition according to claim 1, wherein the ratio (total alcohol component/polybasic acid) is in the range of 1.6 to 2.5.
3.請求項1または2記載の電気絶縁用樹脂組成物を導
体上に塗布、焼付けてなる絶縁電線。
3. An insulated wire obtained by coating and baking the electrically insulating resin composition according to claim 1 or 2 on a conductor.
JP2218518A 1990-08-20 1990-08-20 Resin compound for electric insulation and insulated electric wire Pending JPH04101305A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2218518A JPH04101305A (en) 1990-08-20 1990-08-20 Resin compound for electric insulation and insulated electric wire

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2218518A JPH04101305A (en) 1990-08-20 1990-08-20 Resin compound for electric insulation and insulated electric wire

Publications (1)

Publication Number Publication Date
JPH04101305A true JPH04101305A (en) 1992-04-02

Family

ID=16721189

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2218518A Pending JPH04101305A (en) 1990-08-20 1990-08-20 Resin compound for electric insulation and insulated electric wire

Country Status (1)

Country Link
JP (1) JPH04101305A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5588860A (en) * 1993-08-06 1996-12-31 Sumitomo Wiring Systems, Ltd. Bulb socket

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5588860A (en) * 1993-08-06 1996-12-31 Sumitomo Wiring Systems, Ltd. Bulb socket

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